The role of copper crystallization and segregation toward enhanced methanol synthesis via CO2 hydrogenation over CuZrO2 catalysts: A combined experimental and computational study.

[Display omitted] • The lower CO 2 adsorption was indeed observed through the higher Cu concentration. • Methanol formation rate was induced by amorphous and crystalline copper phases. • Cu-doping model was more suitable surface for the conversion of CO 2 into methanol. The role of copper crystallization in the enhanced methanol production via CO 2 hydrogenation over CuZrO 2 catalysts was explored along with a combination of experimental and computational studies. The catalysts were synthesized by a surfactant-assisted route followed by reflux in a one-pot method. Catalyst structure, bulk properties, surface reactivity, and reaction pathways were evaluated by XRD, BET, FRX, TPR, N 2 O-TPD, CO 2 -TPD, in situ DRIFTS, AP-XPS, and XRD. Calculations based on density functional theory (DFT) were performed to explore the formation of possible intermediates in a copper-driven conversion with surface models of the CuZrO 2 catalyst. The combination of experiments and DFT results revealed that the intermediate steps of the catalyzed reaction of CO 2 hydrogenation into methanol might depend on the incorporation of Cu in the zirconia sample. The catalyst containing only amorphous interfacial sites showed higher performance on CO 2 -to-methanol hydrogenation compared to the catalysts containing high crystallinity of copper. The superior activity of the 10CuZrO 2 catalyst is mainly ascribed to the cooperative effect between the highly dispersed copper nanoparticles and the basic sites. [ABSTRACT FROM AUTHOR]